Process for the production of biodegradable hydrocarbon fluids by hydrogenation

ABSTRACT

The invention provides for a fluid having a boiling point in the range of from 100 to 400° C. and comprising more than 95% isoparaffins and containing less than 100 ppm aromatics, obtainable by the process comprising the step of catalytically hydrogenating a feed comprising more than 95% by weight of a hydrodeoxygenated isomerized hydrocarbon biomass feedstock, at a temperature from 80 to 180° C. and at a pressure from 50 to 160 bars. The invention also provides for a fluid having a boiling point in the range of from 100 to 400° C. and a boiling range below 80° C., said fluid comprising more than 95% isoparaffins and less than 3% of naphthens by weight and having a ratio of isoparaffins to n-paraffins of at least 12:1, a biodegradability at 28 days of at least 60%, as measured according to the OECD 306 standard, a biocarbon content of at least 95% by weight, and containing less than 100 ppm aromatics by weight. The invention finally provides for uses of the fluid.

FIELD OF THE INVENTION

The invention relates to the production of biodegradable hydrocarbonfluids, hereinafter referred to as being improved fluids, having anarrow boiling range and having a very low aromatic content and theiruses. The invention relates to a process for producing these improvedfluids by hydrogenation of HDO/ISO feedstocks.

BACKGROUND ART

Hydrocarbon fluids find widespread use as solvents such as in adhesives,cleaning fluids, solvents for explosives, for decorative coatings andprinting inks, light oils for use in applications such as metalextraction, metalworking or demoulding and industrial lubricants, anddrilling fluids. The hydrocarbon fluids can also be used as extenderoils in adhesives and sealant systems such as silicone sealants and asviscosity depressants in plasticised polyvinyl chloride formulations andas carrier in polymer formulation used as flocculants for example inwater treatment, mining operations or paper manufacturing and also usedas thickener for printing pastes, as plasticizers in tyre materials.Hydrocarbon fluids may also be used as solvents in a wide variety ofother applications such as chemical reactions.

The chemical nature and composition of hydrocarbon fluids variesconsiderably according to the use to which the fluid is to be put.Important properties of hydrocarbon fluids are the distillation rangegenerally determined by ASTM D-86 or the ASTM D-1160 vacuum distillationtechnique used for heavier materials, flash point, density, anilinepoint as determined by ASTM D-611, aromatic content, sulphur content,viscosity, colour and refractive index.

These fluids tend to have narrow boiling point ranges as indicated by anarrow range between Initial Boiling Point (IBP) and Final Boiling Point(FBP) according to ASTM D-86. The Initial Boiling Point and the FinalBoiling Point will be chosen according to the use to which the fluid isto be put. However, the use of the narrow cuts provides the benefit of anarrow flash point and may also prevent the emission of Volatile OrganicCompounds which are important for safety reasons. The narrow cut alsobrings important fluid properties such as a better defined aniline pointor solvency power, then viscosity, and defined evaporation conditionsfor systems where drying is important, and finally better definedsurface tension.

Nowadays, biodegradability is a requirement for these specific fluids.

US2009/0014354 discloses biodegradable cuts boiling at 356-413° C., andcomprising mostly isoparaffins with an amount of naphthenics of not lessthan 7%. The cuts originate from biological origin.

EP2368967 discloses a solvent composition containing 5 to 30% of C₁₀-C₂₀n-alkanes, and 70 to 95% of C₁₀-C₂₀ iso-alkanes, by weight, said solventcomposition being produced from raw materials of biological origin. Thesolvent composition has a boiling range of 180 to 340° C.

WO00/20534 discloses a solvent issued from Fischer-Tropsch synthesis andwhich is typically a biodegradable synthetic middle distillate cut andhas an isoparaffins to n-paraffins mass ratio of between about 1:1 toabout 12:1. The boiling range is above 80° C. A preferred composition isone which has at least 30% (mass) of the isoparaffins as mono-methylbranched.

WO2006/084285 discloses a hydrocarbon fluid composition of syntheticorigin comprising isoparaffins and a minimum initial boiling point tomaximum final boiling point at or within the range of 110° C. to 350° C.and which is said to be biodegradable. The cetane number is said to beless than 60. The applicant is also marketing a composition ISOPAR®,which typically contains more than 20% naphthenic compounds.

US2014/0323777 discloses a process for manufacturing an aviation fueloil base having an isoparaffin content of 80% by weight or more but atmost 91.6%, and an aromatic content of less than 0.1 vol %.

The document “Fluids and Solutions, Isoparaffins, Isane” from Total,(citation from the Internet, pages 1-2,URL:http://www.total.de/shared/ccuri/179/11/ISANE 2011.pdf) discloses acomposition of fluids for use in paints with boiling ranges between 100and 300° C., 100% isoparaffins and an aromatic content of 10 to 50 ppmby weight. The Isane fluid is of fossil origin.

US2012/0283492 discloses a process for hydrogenating a low-sulphur feedinto a fluid having a boiling range of not more than 80° C. and havingan isoparaffin content of at most about 52% by weight.

There is still a need for fluids with high biodegradability and being ofbiological origin.

SUMMARY OF THE INVENTION

The invention provides new hydrocarbon fluids, and especially obtainableby the process of the invention, hereafter “improved fluids”. Theinvention thus provides a fluid having a boiling point in the range offrom 100 to 400° C. and comprising more than 95% isoparaffins andcontaining less than 100 ppm aromatics by weight, obtainable by theprocess comprising the step of catalytically hydrogenating a feedcomprising more than 95% by weight of a hydrodeoxygenated isomerizedhydrocarbon biomass feedstock, at a temperature from 80 to 180° C., at apressure from 50 to 160 bars, a liquid hourly space velocity of 0.2 to 5hr⁻¹ and an hydrogen treat rate up to 200 Nm³/ton of feed.

According to an embodiment, the hydrogenation conditions of the processby which the fluid is obtainable are the following:

-   -   Pressure: 80 to 150 bars, and preferably 90 to 120 bars;    -   Temperature: 120 to 160° C. and preferably 150 to 160° C.;    -   Liquid hourly space velocity (LHSV): 0.4 to 3, and preferably        0.5 to 0.8;

Hydrogen treat rate be up to 200 Nm³/ton of feed.

According to an embodiment, the feed comprises more than 98%, preferablymore than 99% of a hydrodeoxygenated isomerized hydrocarbon biomassfeedstock, and more preferably consists of a hydrodeoxygenatedisomerized hydrocarbon biomass feedstock.

According to an embodiment, the biomass is a vegetable oil, an esterthereof or a triglyceride thereof.

According to an embodiment, a fractionating step is carried out beforethe hydrogenating step, or after the hydrogenating step or both;according to an embodiment, the process comprises three hydrogenationstages, preferably in three separate reactors.

The invention also provides new hydrocarbon fluids, hereafter “improvedfluids”, also referring to the fluids obtained by the process of theinvention.

The invention thus provides fluids having a boiling point in the rangeof from 100 to 400° C. and a boiling range below 80° C., said fluidcomprising more than 95% isoparaffins and less than 3% of naphthens byweight and having a ratio of iso-paraffins to n-paraffins of at least12:1, a biodegradability at 28 days of at least 60%, as measuredaccording to the OECD 306 standard, a biocarbon content of at least 95%by weight, and containing less than 100 ppm aromatics by weight.

According to an embodiment, the fluid has a boiling point in the range150 to 400° C., preferably from 200 to 400° C., especially 220 to 340°C. and advantageously more than 250° C. and up to 340° C.

According to an embodiment, the fluid has a boiling range below 80° C.,preferably below 60° C., advantageously between 40 and 50° C.

According to an embodiment, the fluid contains less than 50 ppmaromatics by weight, and preferably less than 20 ppm by weight.

According to an embodiment, the fluid contains less than 3% by weight ofnaphthens by weight, preferably less than 1% and advantageously lessthan 50 ppm by weight.

According to an embodiment, the fluid contains less than 5 ppm, evenless than 3 ppm and preferably less than 0.5 ppm sulphur.

According to an embodiment, the fluid comprises more than 98%isoparaffins by weight.

According to an embodiment, the fluid has a ratio of iso-paraffins ton-paraffins of at least 12:1, preferably at least 15:1, more preferablyat least 20:1.

According to an embodiment, the fluid has a biodegradability at 28 daysof at least 60%, as measured according to the OECD 306 standard,preferably at least 70% by weight, more preferably at least 75% andadvantageously at least 80%, as measured according to the OECD 306standard.

According to an embodiment, the fluid has a biocarbon content of atleast 95% by weight, preferably at least 97%, more preferably at least98%, and even more preferably about 100%.

Another object of the invention is the use of the improved fluids. Theinvention thus provides for the use of the fluids of the invention, asdrilling fluids, in hydraulic fracturing, in mining, in watertreatments, as industrial solvents, in paints composition, fordecorative coatings, in coating fluids, in car industry, in textileindustry, in metal extraction, in explosives, in oil dispersants, inconcrete demoulding formulations, in adhesives, in printing inks, inmetal working fluids, coating fluids, rolling oils especially foraluminum, as cutting fluids, as rolling oils, as electric dischargemachining (EDM) fluids, rust preventive, industrial lubricants, asextender oils, in sealants such as mastics or polymers especially withsilicone, as viscosity depressants in plasticised polyvinyl chlorideformulations, in resins, in varnishes, as phytosanitary fluid especiallyas crop protection fluids, as adjuvant or excipient in vaccinepreparations, in paint compositions, especially low-odor paints, inpolymers used in water treatment, paper manufacturing or printing pastesespecially as thickener, cleaning and/or degreasing solvents, for slurrypolymerization, in food processing industry, for food grade application,home care, heat-transfer media, shock absorbers, insulation oils,hydraulic oils, gear oils, turbine oils, textile oils and intransmission fluids such as automatic transmission fluids or manual gearbox formulations, and as solvents in chemical reactions includingcrystallization, extraction and fermentation.

DESCRIPTION OF EMBODIMENTS OF THE INVENTION

The feedstock will first be disclosed, then the hydrogenation step andthe associated fractionating step, and finally the improved fluids.

Feedstock.

The feedstock or simply feed is a feed which is the result of a processof hydrodeoxygenation followed by isomerization, hereafter “HDO/ISO”, aspracticed on a biomass.

This HDO/ISO process is applied on biological raw materials, thebiomass, selected from the group consisting of vegetable oils, animalfats, fish oils, and mixtures thereof, preferably vegetable oils.Suitable vegetable raw materials include rapeseed oil, canola oil, colzaoil, tall oil, sunflower oil, soybean oil, hemp oil, olive oil,linenseed oil, mustard oil, palm oil, arachis oil, castor oil, coconutoil, animal fats such as suet, tallow, blubber, recycled alimentaryfats, starting materials produced by genetic engineering, and biologicalstarting materials produced by microbes such as algae and bacteria.Condensation products, esters, or other derivatives obtained frombiological raw materials may also be used as starting materials. Anespecially preferred vegetable raw material is an ester or triglyceridederivative. This material is submitted to an hydrodeoxygenation (HDO)step for decomposing the structure of the biological ester ortriglyceride constituent, and for removing oxygen, phosphorus and sulfur(part of) compounds, concurrently hydrogenating the olefinic bonds,followed by isomerization of the product thus obtained, thus branchingthe hydrocarbon chain and improving the low temperature properties ofthe thus-obtained feedstock.

In the HDO step, hydrogen gas and the biological constituent are passedto the HDO catalyst bed either in countercurrent or concurrent manner.In the HDO step, the pressure and the temperature range typicallybetween 20 and 150 bar, and between 200 and 500° C., respectively. Inthe HDO step, known hydrodeoxygenation catalysts may be used. Prior tothe HDO step, the biological raw material may optionally be subjected toprehydrogenation under milder conditions to avoid side reactions of thedouble bonds. After the HDO step, the product is passed to theisomerization step where hydrogen gas and the biological constituent tobe hydrogenated, and optionally a n-paraffin mixture, are passed to theisomerization catalyst bed either in concurrent or countercurrentmanner. In the isomerization step, the pressure and the temperaturerange between typically 20 and 150 bar, and between 200 and 500° C.,respectively. In the isomerization step, isomerization catalysts knownas such may be typically used.

Secondary process steps can also be present (such as intermediatepooling, scavenging traps, and the like).

The product issued from the HDO/ISO steps may for instance befractionated to give the desired fractions.

Various HDO/ISO processes are disclosed in the literature.WO02014/033762 discloses a process which comprises a pre-hydrogenationstep, a hydrodeoxygenation step (HDO) and an isomerization step whichoperates using the countercurrent flow principle. EP1728844 describes aprocess for the production of hydrocarbon components from mixtures of avegetable or animal origin. The process comprises a pretreatment step ofthe mixture of a vegetable origin for removing contaminants, such as,for example, alkaline metals salts, followed by a hydrodeoxygenation(HDO) step and an isomerization step. EP2084245 describes a process forthe production of a hydrocarbon mixture that can be used as diesel fuelor diesel component by the hydrodeoxygenation of a mixture of abiological origin containing fatty acid esters possibly with aliquots offree fatty acids, such as for example vegetable oils such as sunfloweroil, rape oil, canola oil, palm oil, or fatty oils contained in the pulpof pine trees (tall oil), followed by hydroisomerization on specificcatalysts. EP2368967 discloses such a process and the thus-obtainedproduct.

Feedstocks typically contain less than 15 ppm of sulphur, preferablyless than 8 ppm and more preferably less than 5 ppm, especially lessthan 1 ppm, as measured according to EN ISO 20846. Typically thefeedstocks will comprise no sulphur as being biosourced products.

Before entering the hydrogenation unit, a pre-fractionation step cantake place. Having a more narrow boiling range entering the unit allowshaving a more narrow boiling range at the outlet. Indeed typical boilingranges of pre-fractionated cuts are 220 to 330° C. while cuts without apre-fractionating step typically have a boiling range from 150° C. to360° C.

Hydrogenation Step.

The feedstock issued from HDO/ISO is then hydrogenated. The feedstockcan optionally be pre-fractionated.

Hydrogen that is used in the hydrogenation unit is typically a highpurity hydrogen, e.g. with a purity of more than 99%, albeit othergrades can be used.

Hydrogenation takes place in one or more reactors. The reactor cancomprise one or more catalytic beds. Catalytic beds are usually fixedbeds.

Hydrogenation takes place using a catalyst. Typical hydrogenationcatalysts include but are not limited to: nickel, platinum, palladium,rhenium, rhodium, nickel tungstate, nickel molybdenum, molybdenum,cobalt molybdenate, nickel molybdenate on silica and/or alumina carriersor zeolites. A preferred catalyst is Ni-based and is supported on analumina carrier, having a specific surface area varying between 100 and200 m²/g of catalyst.

The hydrogenation conditions are typically the following:

-   -   Pressure: 50 to 160 bars, preferably 100 to 150 bars;    -   Temperature: 80 to 180° C., preferably 120 to 160° C.;    -   Liquid hourly space velocity (LHSV): 0.2 to 5 hr⁻¹, preferably        0.5 to 3;    -   Hydrogen treat rate: adapted to the above conditions, which can        be up to 200 Nm³/ton of feed.

The hydrogenation process of the invention can be carried out in severalstages. There can be two or three stages, preferably three stages,preferably in three separate reactors. The first stage will operate thesulphur trapping, hydrogenation of substantially all unsaturatedcompounds, and up to about 90% of hydrogenation of aromatics. The flowexiting from the first reactor contains substantially no sulphur. In thesecond stage the hydrogenation of the aromatics continues, and up to 99%of aromatics are hydrogenated. The third stage is a finishing stage,allowing an aromatic content as low as 100 ppm by weight or even lesssuch as below 50 ppm, even for high boiling products.

The catalysts can be present in varying or substantially equal amountsin each reactor, e.g. for three reactors according to weight amounts of0.05-0.5/0.10-0.70/0.25-0.85, preferably 0.07-0.25/0.15-0.35/0.4-0.78and most preferably 0.10-0.20/0.20-0.32/0.48-0.70.

It is also possible to have one or two hydrogenation reactors instead ofthree.

It is also possible that the first reactor be made of twin reactorsoperated alternatively in a swing mode. This may be useful for catalystcharging and discharging: since the first reactor comprises the catalystthat is poisoned first (substantially all the sulphur is trapped inand/or on the catalyst) it should be changed often.

One reactor can be used, in which two, three or more catalytic beds areinstalled.

It may be necessary to insert quenches on the recycle to cool effluentsbetween the reactors or catalytic beds to control reaction temperaturesand consequently hydrothermal equilibrium of the hydrogenation reaction.In a preferred embodiment, there is no such intermediate cooling orquenching.

In case the process makes use of 2 or 3 reactors, the first reactor willact as a sulphur trap. This first reactor will thus trap substantiallyall the sulphur. The catalyst will thus be saturated very quickly andmay be renewed from time to time. When regeneration or rejuvenation isnot possible for such saturated catalyst the first reactor is consideredas a sacrificial reactor which size and catalyst content both depend onthe catalyst renewal frequency.

In an embodiment the resulting product and/or separated gas is/are atleast partly recycled to the inlet of the hydrogenation stages. Thisdilution helps, if this were to be needed, maintaining the exothermicityof the reaction within controlled limits, especially at the first stage.Recycling also allows heat-exchange before the reaction and also abetter control of the temperature.

The stream exiting the hydrogenation unit contains the hydrogenatedproduct and hydrogen. Flash separators are used to separate effluentsinto gas, mainly remaining hydrogen, and liquids, mainly hydrogenatedhydrocarbons. The process can be carried out using three flashseparators, one of high pressure, one of medium pressure, and one of lowpressure, very close to atmospheric pressure.

The hydrogen gas that is collected on top of the flash separators can berecycled to the inlet of the hydrogenation unit or at different levelsin the hydrogenation units between the reactors.

Because the final separated product is at about atmospheric pressure, itis possible to feed directly the fractionation stage, which ispreferably carried out under vacuum pressure that is at about between 10to 50 mbars, preferably about 30 mbars.

The fractionation stage can be operated such that various hydrocarbonfluids can be withdrawn simultaneously from the fractionation column,and the boiling range of which can be predetermined.

Therefore, fractionation can take place before hydrogenation, afterhydrogenation, or both.

The hydrogenation reactors, the separators and the fractionation unitcan thus be connected directly, without having to use intermediatetanks. By adapting the feed, especially the initial and final boilingpoints of the feed, it is possible to produce directly, withoutintermediate storage tanks, the final products with the desired initialand final boiling points. Moreover, this integration of hydrogenationand fractionation allows an optimized thermal integration with reducednumber of equipment and energy savings.

Fluids of the Invention.

The fluids of the invention, especially those produced according to theprocess of the invention, hereafter referred to simply as “the improvedfluids” possess outstanding properties, in terms of aniline point orsolvency power, molecular weight, vapour pressure, viscosity, definedevaporation conditions for systems where drying is important, anddefined surface tension.

The improved fluids are primarily isoparaffinic and contain more than95% isoparaffins by weight, preferably more than 98%.

The improved fluids typically contain less than 3% by weight ofnaphthens, preferably less than 1% and advantageously less than 50 ppmby weight.

The improved fluids typically have a ratio of iso-paraffins ton-paraffins of at least preferably at least 12:1, more preferably atleast 15:1, more preferably more than 20:1.

Typically, the improved fluids comprise carbon atoms number from 6 to30, preferably 8 to 24 and most preferably from 9 to 20 carbon atoms.

The improved fluids have a boiling range from 100 to 400° C. and alsoexhibit an enhanced safety, due to the very low aromatics content.

The improved fluids typically contain less than 100 ppm by weight, morepreferably less than 50 ppm, advantageously less than 20 ppm aromatics(measured using a UV method). This makes them suitable for use in cropprotection fluids. This is especially useful for high temperatureboiling products, typically products boiling in the range 300-400° C.,preferably 320-380° C.

The boiling range of the improved fluids is preferably not more than 80°C., preferably not more than 70° C., more preferably not more than 60°C., advantageously between 40 and 50° C.

The improved fluids also have an extremely low sulphur content,typically less than 5 ppm, even less than 3 ppm and preferably less than0.5 ppm, at a level too low to be detected by the usual low-sulphuranalyzers.

The improved fluids find various uses, including but not limited to: asdrilling fluids, in hydraulic fracturing, in mining, in watertreatments, as industrial solvents, in paints composition, fordecorative coatings, in coating fluids, in car industry, in textileindustry, in metal extraction, in explosives, in oil dispersants, inconcrete demoulding formulations, in adhesives, in printing inks, inmetal working fluids, coating fluids, rolling oils especially foraluminum, as cutting fluids, as rolling oils, as electric dischargemachining (EDM) fluids, rust preventive, industrial lubricants, asextender oils, in sealants such as mastics or polymers especially withsilicone, as viscosity depressants in plasticised polyvinyl chlorideformulations, in resins, in varnishes, as phytosanitary fluid especiallyas crop protection fluids, as adjuvant or excipient in vaccinepreparations, in paint compositions, especially low-odor paints, inpolymers used in water treatment, paper manufacturing or printing pastesespecially as thickener, cleaning and/or degreasing solvents, for slurrypolymerization, in food processing industry, for food grade application,home care, heat-transfer media, shock absorbers, insulation oils,hydraulic oils, gear oils, turbine oils, textile oils and intransmission fluids such as automatic transmission fluids or manual gearbox formulations, and as solvents in chemical reactions includingcrystallization, extraction and fermentation.

In all this foreseen uses, the Initial Boiling Point (IBP) to FinalBoiling Point (FBP) range is selected according to the particular useand composition. An Initial Boiling Point of more than 250° C. allowsclassification as free of VOC (Volatile Organic Compound) according tothe directive 2004/42/CE.

The isoparaffinic nature of the improved fluids allows for improved lowtemperature properties.

The improved fluids are also useful as components in adhesives, sealantsor polymer systems such as silicone sealant, modified silane polymerswhere they act as extender oils and as viscosity depressants forpolyvinyl chloride (PVC) pastes or Plastisol formulations.

The improved fluids may also be used as new and improved solvents,particularly as solvents for resins. The solvent-resin composition maycomprise a resin component dissolved in the fluid, the fluid comprising5 to 95% by total volume of the composition.

The improved fluids may be used in place of solvents currently used forinks, coatings and the like.

The improved fluids may also be used to dissolve resins such as:acrylic-thermoplastic, acrylic-thermosetting, chlorinated rubber, epoxy(either one or two part), hydrocarbon (e.g., olefins, terpene resins,rosin esters, petroleum resins, coumarone-indene, styrene-butadiene,styrene, methyl-styrene, vinyl-toluene, polychloroprene, polyamide,polyvinyl chloride and isobutylene), phenolic, polyester and alkyd,polyurethane and modified polyurethane, silicone and modified silicone(MS polymers), urea, and, vinyl polymers and polyvinyl acetate.

Examples of the type of specific applications for which the improvedfluids and fluid-resin blends may be used include coatings, cleaningcompositions and inks. For coatings the blend preferably has high resincontent, i.e., a resin content of 20% to 80% by volume. For inks, theblend preferably contains a lower concentration of the resin, i.e.,5%-30% by volume.

In yet another embodiment, various pigments or additives may be added.

The improved fluids can be used as cleaning compositions for the removalof hydrocarbons

The improved fluids may also be used in cleaning compositions such asfor use in removing ink, more specifically in removing ink fromprinting.

In the offset printing industry it is important that ink can be removedquickly and thoroughly from the printing surface without harming themetal or rubber components of the printing machine. Further there is atendency to require that the cleaning compositions are environmentallyfriendly in that they contain no or hardly any aromatic volatile organiccompounds and/or halogen containing compounds. A further trend is thatthe compositions fulfil strict safety regulations. In order to fulfilthe safety regulations, it is preferred that the compositions have aflash point of more than 62° C., more preferably a flash point of 90° C.or more. This makes them very safe for transportation, storage and use.The improved fluids have been found to give a good performance in thatink is readily removed while these requirements are met.

The improved fluids are also useful as drilling fluids, such as adrilling fluid which has the fluid prepared by the process of thisinvention as a continuous oil phase. The improved fluids may also beused as a penetration rate enhancer comprising a continuous aqueousphase containing the improved fluid dispersed therein.

Fluids used for offshore or on-shore applications need to exhibitacceptable biodegradability, human, eco-toxicity, eco-accumulation andlack of visual sheen credentials for them to be considered as candidatefluids for the manufacturer of drilling fluids. In addition, fluids usedin drilling uses need to possess acceptable physical attributes. Thesegenerally include a viscosity of less than 4.0 mm²/s at 40° C., a flashvalue of usually more than 90° C. and, for cold weather applications, apour point at −40° C. or lower. These properties have typically beenonly attainable through the use of expensive synthetic fluids such ashydrogenated polyalphaolefins, as well as unsaturated internal olefinsand linear alpha-olefins and esters. The properties can now be obtainedin the improved fluids.

Drilling fluids may be classified as either water-based or oil-based,depending upon whether the continuous phase of the fluid is mainly oilor mainly water. Water-based fluids may however contain oil andoil-based fluids may contain water and the fluids produced according tothe process of the invention are particularly useful as the oil phase.

Typically preferred ASTM D-86 boiling ranges for the uses of the fluidsare that of printing ink solvents (sometimes known as distillates) haveboiling ranges in the ranges of 235° C. to 265° C., 260° C. to 290° C.,280° C. to 315° C. and 300° C. to 355° C. Fluids preferred for use asdrilling fluids have boiling ranges in the ranges of 195° C. to 240° C.,235° C. to 265° C. and 260° C. to 290° C. Fluids preferred forexplosives, concrete demoulding, industrial lubricants, transmissionfluids and metal working fluids have boiling ranges in the ranges of185° C. to 215° C., 195° C. to 240° C., 235° C. to 365° C., 260° C. to290° C., 280° C. to 325° C. and 300° C. to 360° C. Fluids preferred asextenders for sealants have boiling ranges in the ranges of 195° C. to240° C., 235° C. to 265° C., 260° C. to 290° C., 280° C. to 325° C. or300° C. to 360° C. Fluids preferred as viscosity depressants forpolyvinyl chloride plastisols have boiling ranges in the ranges of 185°C. to 215° C., 195° C. to 240° C., 235° C. to 265° C., 260° C. to 290°C., 280° C. to 315° C. and 300° C. to 360° C.

Fluids preferred as carrier for polymeric composition used in watertreatment, mining operation or printing pastes have boiling ranges inthe ranges of 185° C. to 215° C., 195° C. to 240° C., 235° C. to 265°C., 260° C. to 290° C., 280° C. to 315° C. and 300° C. to 360° C.

Fluids preferred for crop protection application have boiling ranges inthe range of 300 and 370° C., such fluids being used in combination withhydrocarbon fluids such as isodewaxed hydrocarbons or any hydrocarbonshaving comparable properties such as viscosity.

For paint compositions and cleaning applications, the most preferredboiling ranges are in the ranges of 140 to 210° C., and 180 to 220° C.Fluids showing an initial boiling point above 250° C. and a finalboiling point close to 330° C. or preferably close to 290° C. will bepreferred for low VOC coatings formulations.

Biodegradation of an organic chemical refers to the reduction incomplexity of the chemical through metabolic activity of microorganisms.Under aerobic conditions, microorganisms convert organic substances intocarbon dioxide, water and biomass. OECD 306 method, is available forassessing biodegradability of individual substances in seawater. OECDMethod 306 can be carried out as either a shake flask or Closed Bottlemethod and the only microorganisms added are those microorganisms in thetest seawater to which the test substance is added. In order to assessthe biotic degradation in seawater, a biodegradability test wasperformed which allows the biodegradability to be measured in seawater.The biodegradability was determined in the Closed Bottle test performedaccording to the OECD 306 Test Guidelines. The biodegradability of theimproved fluids is measured according to the OECD Method 306.

The OECD Method 306 is the following:

The closed bottle method consists on dissolution of a pre-determinedamount of the test substance in the test medium in a concentration ofusually 2-10 mg/l, with one or more concentrations being optionallyused. The solution is kept in a filled closed bottle in the dark in aconstant temperature bath or enclosure controlled within a range of15-20° C. The degradation is followed by oxygen analyses over a 28-dayperiod. Twenty-four bottles are used (8 for test substance, 8 forreference compound and 8 for sweater plus nutriment). All analyses areperformed on duplicate bottles. Four determinations of dissolved oxygen,at least, are performed (day 0, 5, 15 and 28) using a chemical orelectrochemical method.

Results are thus expressed in % degradability at 28 days. The improvedfluids have a biodegradability at 28 days of at least 60%, as measuredaccording to the OECD 306 standard, preferably at least 70% by weight,more preferably at least 75% and advantageously at least 80%.

The invention uses the products of natural origin like startingproducts. The carbon of a biomaterial comes from the photosynthesis ofthe plants and thus of atmospheric CO₂. The degradation (by degradation,one will understand also combustion/incineration at the end of thelifetime) of these CO2 materials thus does not contribute to the warmingsince there is no increase in the carbon emitted in the atmosphere. Theassessment CO₂ of the biomaterials is thus definitely better andcontributes to reduce the print carbon of the products obtained (onlyenergy for manufacture is to be taken into account). On the contrary, afossil material of origin being also degraded out of CO₂ will contributeto the increase in the CO₂ rate and thus to climate warming. Theimproved fluids according to the invention will thus have a print carbonwhich will be better than that of compounds obtained starting from afossil source.

The invention thus improves also the ecological assessment during themanufacture of the improved fluids. The term of “bio-carbon” indicatesthat carbon is of natural origin and comes from a biomaterial, asindicated hereafter. The content of biocarbon and the content ofbiomaterial are expressions indicating the same value.

A renewable material of origin or biomaterial is an organic material inwhich carbon comes from CO₂ fixed recently (on a human scale) byphotosynthesis starting from the atmosphere. On ground, this CO₂ iscollected or fixed by the plants. At sea, CO₂ is collected or fixed bymicroscopic bacteria or plants or algae carrying out a photosynthesis. Abiomaterial (carbon natural origin 100%) presents an isotopic ratio¹⁴C/¹²C higher than 10⁻¹², typically about 1.2×10⁻¹², while a fossilmaterial has a null ratio. Indeed, the isotope ¹⁴C is formed in theatmosphere and is then integrated by photosynthesis, according to ascale of time of a few tens of years at the maximum. The half-life of¹⁴C is 5730 years. Thus the materials resulting from photosynthesis,namely the plants in a general way, have necessarily a maximum contentof isotope ¹⁴C.

The determination of the content of biomaterial or content of biocarbonis given pursuant to standards ASTM D 6866-12, method B (ASTM D 6866-06)and ASTM D 7026 (ASTM D 7026-04). Standard ASTM D 6866 concerns“Determining the Biobased Content of Natural Range Materials UsingRadiocarbon and Isotope Ratio Mass Spectrometry Analysis”, whilestandard ASTM D 7026 concerns “Sampling and Reporting of Results forDetermination of Biobased Content of Materials via Carbon IsotopeAnalysis”. The second standard mentions the first in its firstparagraph.

The first standard describes a test of measurement of the ratio ¹⁴C/¹²Cof a sample and compares it with the ratio ¹⁴C/¹²C of a sample renewablereference of origin 100%, to give a relative percentage of C of originrenewable in the sample. The standard is based on the same concepts thatthe dating with ¹⁴C, but without making application of the equations ofdating. The ratio thus calculated is indicated as the “pMC” (percentModem Carbon). If the material to be analyzed is a mixture ofbiomaterial and fossil material (without radioactive isotope), then thevalue of pMC obtained is directly correlated with the quantity ofbiomaterial present in the sample. The value of reference used for thedating to ¹⁴C is a value dating from the years 1950. This year wasselected because of the existence of nuclear tests in the atmospherewhich introduced great quantities of isotopes into the atmosphere afterthis date. The reference 1950 corresponds to a value pMC of 100. Takinginto account the thermonuclear tests, the current value to be retainedis approximately 107.5 (what corresponds to a factor of correction of0.93). The signature into radioactive carbon of a current plant is thusof 107.5. A signature of 54 pMC and 99 pMC thus correspond to a quantityof biomaterial in the sample of 50% and 93%, respectively.

The compounds according to the invention come at least partly frombiomaterial and thus present a content of biomaterial from at least 95%.This content is advantageously even higher, in particular more than 98%,more preferably more than 99% and advantageously about 100%. Thecompounds according to the invention can thus be bio-carbon of 100%biosourced or on the contrary to result from a mixture with a fossilorigin. According to an embodiment, the isotopic ratio ¹⁴C/¹²C isbetween 1.15 and 1.2×10⁻¹².

All percentages and ppm are by weight unless indicated to the contrary.Singular and plural are used interchangeably to designate the fluid(s).

Example

The following example illustrates the present invention withoutlimitation.

A feedstock being a feedstock of a kerosene, obtained a process thatconverts liquid lipid sources (vegetal oil, animal fats etc.) thanks tothe steps of hydrotreatment, hydrocracking and isomerization, is used inthe process of the invention. This kerosene had an aromatic content of1000 ppm.

The following conditions for hydrogenation are used:

The temperature in the reactors is about 150-160° C.; the pressure isabout 100 bars and the liquid hourly space velocity is 0.6 h⁻¹; thetreat rate is adapted. The catalyst used is nickel on alumina.

The resulting product is obtained, with the following properties.

Characteristic Ex. 1 Aromatic content (ppm) <20 Sulfur content (ppm) 0.1% isoparaffins (w/w) 96.2 % n-paraffins (w/w) 3.8 % naphthenic (w/w) 0C8 (iso) 1.46 C9 (iso) 6.49 C10 (iso) 7.99 C11 (iso) 8.23 C12 (iso) 7.81C13 (iso) 6.55 C14 (iso) 4.84 C15 (iso) 7.07 C16 (iso) 28.49 C17 (iso)1.89 C18 (iso) 15.4 C quat sat 0.0 CH sat 13.7 CH₂ sat 62.4 CH₃ sat 23.7CH₃ long chain 16.2 CH₃ short chain 7.6 Biocarbon content (%) 100.0Initial Boiling Point (° C.) 120.6 5% point (° C.) 144.1 50% point (°C.) 260.5 95% point (° C.) 301.7 Dry point (° C.) 311.1 OECDbiodegradability (28 days) (%) 80

These results show that the product prepared according to the process ofthe invention is free of sulphur and exhibits a very low aromaticcontent, and is isoparaffinic in nature. Its specific branchingdistribution and ultra low aromatics content allow for biodegradabilityand compliance with stringent regulations. Its properties make it verysuitable for hydrocarbon fluid applications as special fluids.

1. Fluid having a boiling point in the range of from 100 to 400° C. andcomprising more than 95% isoparaffins and containing less than 100 ppmaromatics by weight, obtainable by the process comprising the step ofcatalytically hydrogenating a feed comprising more than 95% by weight ofa hydrodeoxygenated isomerized hydrocarbon biomass feedstock, at atemperature from 80 to 180° C., at a pressure from 50 to 160 bars, aliquid hourly space velocity of 0.2 to 5 h⁻¹ and an hydrogen treat rateup to 200 Nm³/ton of feed.
 2. Fluid of claim 1, obtainable by theprocess wherein the hydrogenation conditions are the following:Pressure: 80 to 150 bars, and preferably 90 to 120 bars; Temperature:120 to 160° C. and preferably 150 to 160° C.; Liquid hourly spacevelocity (LHSV): 0.4 to 3, and preferably 0.5 to 0.8; Hydrogen treatrate be up to 200 Nm³/ton of feed.
 3. Fluid of claim 1, wherein the feedcomprises more than 98%, preferably more than 99% of a hydrodeoxygenatedisomerized hydrocarbon biomass feedstock, and more preferably consistsof a hydrodeoxygenated isomerized hydrocarbon biomass feedstock. 4.Fluid of claim 1, wherein the biomass is a vegetable oil, an esterthereof or a triglyceride thereof.
 5. Fluid of claim 1, wherein (i) afractionating step is carried out before the hydrogenating step, orafter the hydrogenating step or both, or (ii) the process comprisesthree hydrogenation stages, preferably in three separate reactors, or(iii) both (i) and (ii).
 6. Fluid of claim 1, having a boiling point inthe range of from 100 to 400° C. and a boiling range below 80° C., saidfluid comprising more than 95% isoparaffins and less than 3% ofnaphthens by weight and having a ratio of isoparaffins to n-paraffins ofat least 12:1, a biodegradability at 28 days of at least 60%, asmeasured according to the OECD 306 standard, a biocarbon content of atleast 95% by weight, and containing less than 100 ppm aromatics byweight.
 7. Fluid of claim 1, having a boiling point in the range 150 to400° C., preferably from 200 to 400° C., especially 220 to 340° C. andadvantageously more than 250° C. and up to 340° C.
 8. Fluid of claim 1,having a boiling range below 80° C., preferably below 60° C.,advantageously between 40 and 50° C.
 9. Fluid of claim 1, containingless than 50 ppm aromatics by weight, and preferably less than 20 ppm byweight.
 10. Fluid of claim 1 any one of claims 1 to 9, containing lessthan 3% by weight of naphthens, preferably less than 1% andadvantageously less than 50 ppm by weight.
 11. Fluid of claim 1,comprising more than 98% isoparaffins by weight.
 12. Fluid of claim 1,having a ratio of iso-paraffins to n-paraffins of at least 12:1,preferably at least 15:1, more preferably at least 20:1.
 13. Fluid ofclaim 1, having a biodegradability at 28 days of at least 60%,preferably at least 70%, more preferably at least 75% and advantageouslyat least 80%, as measured according to the OECD 306 standard.
 14. Fluidof claim 1, having a biocarbon content of at least 95% by weight,preferably at least 97%, more preferably at least 98%, and even morepreferably about 100%.
 15. Use of the fluids according to claim 1, asdrilling fluids, in hydraulic fracturing, in mining, in watertreatments, as industrial solvents, in paints composition, fordecorative coatings, in coating fluids, in car industry, in textileindustry, in metal extraction, in explosives, in oil dispersants, inconcrete demoulding formulations, in adhesives, in printing inks, inmetal working fluids, coating fluids, rolling oils especially foraluminum, as cutting fluids, as rolling oils, as electric dischargemachining (EDM) fluids, rust preventive, industrial lubricants, asextender oils, in sealants such as mastics or polymers especially withsilicone, as viscosity depressants in plasticised polyvinyl chlorideformulations, in resins, in varnishes, as phytosanitary fluid especiallyas crop protection fluids, as adjuvant or excipient in vaccinepreparations, in paint compositions, especially low-odor paints, inpolymers used in water treatment, paper manufacturing or printing pastesespecially as thickener, cleaning and/or degreasing solvents, for slurrypolymerization, in food processing industry, for food grade application,home care, heat-transfer media, shock absorbers, insulation oils,hydraulic oils, gear oils, turbine oils, textile oils and intransmission fluids such as automatic transmission fluids or manual gearbox formulations, and as solvents in chemical reactions includingcrystallization, extraction and fermentation.